Homopolymers of sulfonated isoprene and 1,3-butadiene and agents containing the same

ABSTRACT

A conjugated diene sulfonation product represented by the formula (I): ##STR1## wherein R 1  to R 6 , which may be the same or different, represent hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, aryl groups having 6 to 20 carbon atoms or --SO 3  X groups (X represents a hydrogen atom, a metal atom, an ammonium group or a quaternary ammonium group), at least one of said R 1  to R 6  being the --SO 3  X group, a polymer of the conjugated diene sulfonation product or a copolymer of the conjugated diene sulfonation product with a monomer copolymerizable therewith. The sulfonation product, the polymer and the copolymer are useful as a dispersing agent for preparing a solid fuel dispersion, a cement dispersion, a dye and/or pigment dispersion or a metal oxide dispersion or as a water-treating agent, a fiber-treating agent, a plating bath additive and an excavation-muddy water-viscosity-adjusting agent.

This application is a continuation of application Ser. No. 07/333,027,filed on Apr. 4, 1989, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a water-soluble or hydrophilic sulfonationproduct of a conjugated diene, a polymer of the sulfonation product anda dispersion of a dispersoid in an aqueous medium in which thesulfonation product or the polymer is used as a dispersing agent.

2. Discussion of the Background

Known water-soluble and/or hydrophilic monomers are those having acarboxyl group such as acrylic acid, methacrylic acid and the like;those having a sulfonic acid group such as allylsulfonic acid,vinylsulfonic acid and the like; etc.

Also, sodium, potassium and lithium salts of the above monomers areknown to be radically polymerizable.

Water-soluble polymers or hydrophilic polymers can be produced bypolymerizing the above monomers or their salts alone or copolymerizingthem with other monomers, and are used widely in industry. For example,polyacrylic acids are used as a dispersing agent for calcium carbonateand partially crosslinked products thereof are used as water-absorbentgels.

Moreover, there are many cases in which acrylic acid and/or methacrylicacid is copolymerized with other vinyl monomers for the purpose ofmodifying rubbers and resins. Further, acrylic acid and/or methacrylicacid is copolymerized with latexes for modifying the latter.

However, these acidic monomers such as acrylic acid, methacrylic acidand the like are weakly acidic though rich in radical-polymerizability,and the polymers obtained therefrom are disadvantageous in that theiremulsifying powers are weak when they are used as surfactants.

On the other hand, vinylsulfonic acid, allylsulfonic acid,methacrylsulfonic acid obtained by reacting isobutylene with sulfurtrioxide, and the like are alkenyl monomers having a strongly acidicsulfonic acid group, and polymers thereof are strongly acidic andexcellent in emulsifying power. However, the monomers per se are poor inradical-polymerizability and give only a low polymer yield and thepolymers produced therefrom have only a low molecular weight.

In addition, there have been developed monomers having a sulfonic acidgroup, such as styrenic monomers, for example, sodium p-styrenesulfonateand the like (e.g., Spinomer, a trade name of Toso Co., Ltd.) andmethacrylic monomers represented by the formula: ##STR2## (e.g.,Eleminol RS-30, a trade name of Sanyo Kasie K.K.).

These monomers have a large molecular weight and a small sulfonic acidgroup content per unit weight though they are strongly acidic andexcellent radical-polymerizability. In addition, the synthesis of themonomers is effected via many steps, and hence, the production processis complicated and expensive.

Therefore, the ion-exchange capacity of the polymer obtained therefromis low and the commercial productivity of the polymer is inferior andthe production cost thereof is high. Thus, the uses thereof areinevitably limited.

The present inventors have made extensive research to solve the aboveproblems of prior art, and as a result, have found that a specificcompound having a sulfonic acid group which is strongly acidic canachieve the above purpose.

An object of this invention is to provide a specific compound having asulfonic acid group which is strongly acidic.

Another object of the invention is to provide a high molecular weightpolymer having a large ion-exchange capacity and a sulfonic acid group.

A further object of the invention is to provide a dispersing agentconsisting essentially of such a specific compound and/or such a highmolecular weight polymer.

A still further object of the invention is to provide a solid fueldispersion, a cement dispersion, a dye and/or pigment dispersion, ametal oxide dispersion, a water-treating agent, a fiber-treating agent,a plating bath additive or an excavation muddy water-treating agent, ineach of which such a dispersing agent is used.

A still another object of the invention is to provide a water-absorbentcrosslinked resin derived from the specific polymer and a compositioncomprising the same.

BRIEF DESCRIPTION OF THE DRAWINGS

Other objects and advantages of this invention will become apparent fromthe following description and the accompanying drawings, in which FIG. 1shows a nuclear magnetic resonance of the polymer obtained in Example 1,FIG. 2 shows an infrared absorption spectrum of the polymer, FIG. 3shows a nuclear magnetic resonance of the polymer obtained in Example 2,FIG. 4 shows an infrared absorption spectrum of the polymer, and FIG. 5shows GPC charts of the polymer obtained in Example 1 and the copolymerobtained in Example 5.

SUMMARY OF THE INVENTION

According to this invention, there is provided a sulfonation product ofa conjugated diene represented by the formula (I) (hereinafter referredto as merely "the sulfonation product"): ##STR3## wherein R¹ to R⁶,which may be the same or different, represent hydrogen atoms, alkylgroups having 1 to 8 carbon atoms, aryl groups having 6 to 20 carbonatoms or --SO₃ X groups [X represents a hydrogen atom, a metal atom(preferably an alkali metal atom or an alkaline earth metal atom, morepreferably a sodium atom or an alkaline earth metal atom), an ammoniumgroup or a quaternary ammonium group], at least one of said R¹ to R⁶being the --SO₃ X group.

This invention further provides a polymer or copolymer of a conjugateddiene sulfonation product (hereinafter referred to as "the sulfonationproduct polymer") obtained by subjecting the sulfonation product of theformula (I) alone or with a copolymerizable monomer to radical oranionic polymerization.

The sulfonation product and the sulfonation product polymer can be usedas a dispersing agent for preparing a solid fuel dispersion, a cementdispersion, a dye and/or pigment dispersion or a metal oxide dispersionor as a water-treating agent, a fiber-treating agent, a plating bathadditive and an excavation-muddy water-viscosity-adjusting agent.

The sulfonation product of this invention is a compound by introducing asulfonic acid group into a conjugated diene, leaving the two doublebonds of the conjugated diene as they are.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In this invention, the conjugated diene used

in the sulfonation product is represented by the formula (II): ##STR4##wherein R's may be the same or different and represent hydrogen atoms,alkyl groups having 1 to 8 carbon atoms or aryl groups having 6 to 20carbon atoms, and includes, for example, 1,3-butadiene, 1,2-butadiene,1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene,1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene,2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene,1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4-heptadiene,2,5-heptadiene, 3,4-heptadiene, 3,5-heptadiene, 2-phenylbutadiene andthe like. It further includes various branched dienes.

The conjugated dienes may be used alone or in admixture of two or more.

The sulfonation product of this invention can be prepared by thefollowing method:

A conjugated diene of the formula (II) is sulfonated with sulfurtrioxide as a sulfonating agent under such known conditions as describedin Jikken Kagaku Koza edited by Chemical Society of Japan, and thecyclic compound thus formed is neutralized.

In this case, sulfur trioxide is used as such or in the form of acomplex with an electron-donating compound.

The electron-donating compound includes N,N-dimethylformamide; etherssuch as dioxane, dibutyl ether, tetrahydrofuran, diethyl ether and thelike; amines such as pyridine, piperazine, trimethylamine,triethylamine, tributylamine and the like; dialkyl sulfides such asdimethyl sulfide, diethyl sulfide and the like; and nitrile compoundssuch as acetonitrile, propionitrile, butyronitrile and the like. Ofthese compounds, N,N-dimethylformamide and dioxane are preferred.

The amount of the sulfonating agent used is 0.1 to 10 moles, preferably0.5 to 3 moles, in terms of sulfur trioxide, per mole of the conjugateddiene. When the amount is less than 0.1 mole, the yield is low, whilewhen it exceeds 10 moles, unreacted sulfur trioxide remains much. Hence,when the reaction mixture is neutralized with an alkali, a large amountof sodium sulfate results, and the purity is consequently lowered.

In the above sulfonation, a solvent inert to the sulfonating agent maybe used, and this solvent includes, for example, halogenatedhydrocarbons such as dichloroethane, tetrachloroethane,tetrachloroethylene, dichloromethane and the like; nitro compounds suchas nitromethane, nitrobenzene and the like; liquid sulfur dioxide;aliphatic hydrocarbons such as propane, butane, pentane, hexane,cyclohexane and the like. These solvents may be used alone or inadmixture of two or more.

The sulfonation temperature is usually -70° to 200° C., preferably -30°to 50° C., and when it is lower than -70° C., the sulfonation becomesslow and is not economical. When it exceeds 200° C., a side reactiontakes place and the product becomes black in some cases.

The above sulfonation produces a cyclic intermediate in which sulfurtrioxide is cyclically bonded to the conjugated diene (cyclic sulfonicacid ester of conjugated diene, the general name thereof being sultone)(hereinafter referred to as the cyclic intermediate).

The sulfonation product represented by the formula (I) is formed byreacting a basic compound with the cyclic intermediate to change thecyclic bond into a double bond having bonded thereto a sulfonic acidgroup (hereinafter referred to as the change into a double bond).

The above basic compound includes alkali metal hydroxides such as sodiumhydroxide, potassium hydroxide, lithium hydroxide and the like; alkalimetal carbonates such as potassium carbonate, sodium carbonate, sodiumhydrogencarbonate, lithium carbonate and the like; alkali metalalkoxides such as sodium methoxide, sodium ethoxide, potassiummethoxide, sodium t-butoxide, potassium t-butoxide and the like;organometallic compounds such as methyllithium, ethyllithium,n-butyllithium, sec-butyllithium, amyllithium, propylsodium,methylmagnesium chloride, ethylmagnesium bromide, propylmagnesiumiodide, diethylgamnesium, diethylzinc, triethylaluminum,triisobutylaluminum and the like; ammonia; water; amines such astrimethylamine, triethylamine, tripropylamine, tributylamine, pyridine,piperazine and the like; metals such as sodium, lithium, potassium,calcium, zinc and the like. These basic compounds may be used alone orin combination of two or more. Among the basic compounds, alkali metalhydroxides are preferable, and sodium hydroxide is particularlypreferable.

The amount of the basic compound used is usually 0.1 to 3 moles,preferably 0.5 to 3 moles, per mole of the conjugated diene. When theamount is less than 0.1 mole, the change of the cyclic bond into adouble bond is not accelerated and the cyclic compound remains as it is,or a hydroxyolefin represented by the following formula is formed, as aresult of which a compound having substantially no polymerizability isproduced: ##STR5##

On the other hand, when the amount exceeds 10 moles, much unreactedalkali remains to reduce the purity of the product.

In the change of the cyclic bond into a double bond, the above basiccompound may be used in solution in water or in an organic solvent inertto the basic compound.

This organic solvent includes the various organic solvents mentionedabove; aromatic hydrocarbons such as benzene, toluene, xylene and thelike; alcohols such as methanol, ethanol, propanol, isopropanol,ethylene glycol and the like; etc. These solvents may be used alone orin admixture of two or more.

When the basic compound is used in solution in water or in solution inan organic solvent, the concentration of the basic compound is usually 1to 70% by weight, preferably 10 to 50% by weight.

The reaction temperature for the change into a double bond is usually-30° to 150° C., preferably -10° to 70° C., and the reaction may beeffected either at atmospheric pressure, under reduced pressure or underpressure.

The reaction time for the change into a double bond is usually 0.1 to 24hours, preferably 0.5 to 5 hours.

In the change into a double bond, water or an alcohol may be added tothe cyclic intermediate to open the ring into a hydroxysulfonic acid oran alkoxysulfonic acid, respectively, which is then subjected todehydration or dealcoholization to obtain the objective sulfonationproduct of the formula (I).

The kind of the cation of the sulfonation product of the formula (I)thus obtained is not critical, and in order to make the sulfonationproduct water-soluble, the cation is preferably hydrogen ion, alkalimetal ion, alkaline earth metal ion, ammonium ion or quaternary ammoniumion.

The above alkali metal ion includes sodium ion, potassium ion and thelike; the alkaline earth metal ion includes calcium ion, magnesium ionand the like; and the quaternary ammonium ion includestetraalkylammonium ions such as tetramethylammonium ion,tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ionand the like.

These cations can be exchanged with other ions by various ion-exchangetechniques.

The sulfonation product polymer of this invention is obtained bypolymerizing the sulfonation product of the formula (I) alone orcopolymerizing it with at least one other monomer copolymerizabletherewith (hereinafter referred to as the copolymerizable monomer) in aproportion of 99% by weight or less, preferably 1 to 98% by weight andmore preferably 10 to 90% by weight.

The copolymerizable monomer includes aromatic alkenyl compounds such asstyrene, α-methylstyrene, vinyltoluene, p-methylstyrene and the like;alkyl and hydroxyalkyl esters of acrylic and methacrylic acids such asmethyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate and the like; acrylic and methacrylic estersof polyethylene glycol, polypropylene glycol, copolymers of ethyleneglycol and propylene glycol and the like; ethylenically unsaturatedmono- and di-carboxylic acids such as acrylic acid, methacrylic acid,crotonic acid, maleic acid, fumaric acid, itaconic acid and the like;anhydrides of the ethylenically unsaturated dicarboxylic acids;aliphatic conjugated dienes such as butadiene, isoprene,2-chloro-1,3-butadiene, 1-chloro-1,3-butadiene and the like;alkenylcyanides such as acrylonitrile, methacrylonitrile and the like;vinyl chloride; vinylidene chloride; vinylmethyl ethyl ketone; vinylmethyl ether; vinyl acetate; vinyl formate; allyl acetate; methallylacetate; acrylamide; methacrylamide; N-methylol acrylamide; glycidylacrylate; glycidyl methacrylate; acrolein; allyl alcohol; ethylenicallyunsaturated sulfonic acids such as styrenesulfonic acid,methacrylsulfonic acid, vinylsulfonic acid, acrylamido-2-propanesulfonicacid, allyllsulfonic acid and the like; and salts of the sulfonic acids;etc.

The sulfonation product polymer of this invention can be prepared bysubjecting to radical polymerization the sulfonation product of theformula (I) and optionally the copolymerizable monomer in apolymerization solvent such as water or an organic solvent in thepresence of a radical polymerization initiator, a chain transfer agentand the like.

The organic solvent for the radical polymerization includes, forexample, alcohols such as methanol, ethanol, isopropanol and the like;aromatic hydrocarbons such as xylene, toluene, benzene and the like;aliphatic hydrocarbons such as butane, pentane, hexane, cyclohexane,heptane and the like.

Among the above polymerization solvents, preferred are water andmethanol.

The radical polymerization initiator includes inorganic initiators, forexample, hydrogen peroxide and persulfate type initiators such aspotassium persulfate, sodium persulfate, ammonium persulfate and thelike; and organic initiators, for example, organic peroxides such ascumene hydroperoxide, isopropylbenzene hydroperoxide, paramenthanehydroperoxide, benzoyl peroxide and the like and azo type initiatorssuch as azobisisobutyronitrile and the like.

The amount of the radical polymerization initiator used is 0.01 to 10parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts byweight in total of the monomers.

The chain transfer agent includes mercaptans such as t-dodecylmercaptan, octyl mercaptan, n-tetradecyl mercaptan, octyl mercaptan,t-hexyl mercaptan, n-hexyl mercaptan and the like; and halogenatedcompounds such as carbon tetrachloride, ethylene bromide and the like.The chain transfer agent is usually used in an amount of 0.001 to 10parts by weight per 100 parts by weight in total of the monomers.

In order to accelerate the radical polymerization, there may be used,together with the initiator, a reducing agent such as sodiumpyrobisulfite, sodium sulfite, sodium hydrogensulfite, ferrous sulfate,glucose, formaldehyde-sodium sulfoxylate, L-ascorbic acid, L-ascrobicacid salts and the like; and chelating agents such as glycine, alanine,sodium ehylenediaminetetraacetate and the like.

In the radical polymerization, various electrolytes, pH-adjustors andthe like may, optionally, be used together with the radical initiatorand the chain transfer agent, and the radical polymerization is effectedin 50 to 1,000 parts by weight of water or the organic solvent per 100parts by weight in total of the monomers in the presence of theabove-mentioned amounts of the radical initiator, the chain transferagent and the like at a temperature of -50° to 200° C., preferably 0° to150° C. for a period of 0.1 to 4 hours.

The monomer mixture comprising the sulfonation product as the essentialcomponent may be added either at one time, continuously or in portionsthough the addition method is not critical.

The final polymerization conversion in the production of the sulfonationproduct polymer is preferably at least 10%, more preferably at least30%.

The polymerization method in this invention is not limited to theabove-mentioned radical polymerization, and the objective sulfonationproduct polymer can be obtained by a conventional anionicpolymerization, too.

The sulfonation product polymer of this invention has at least one ofthe recurring structural units represented by the formulas (III), (IV)and (V): ##STR6## wherein R¹ to R⁶ have the same meanings as definedabove.

The poly(sodium styrenesulfonate)-reduced weight average molecularweight of the sulfonation product polymer of this invention is notuniquely determined; however, it is usually 500 to 5,000,000, preferably1,000 to 500,000.

The sulfonation product polymer of this invention can be converted fromits acid form to a form of salt with alkali metal, alkaline earth metal,ammonium group or quaternay ammonium group or from its salt form to theacid form or another salt form by an ion-exchange method, aneutralization reaction or the like.

Also, when the sulfonation product polymer thus obtained has a freesulfonic acid group or groups, the sulfonation product polymer isneutralized with an aqueous alkali solution such as aqueous sodiumhydroxide, aqueous potassium hydroxide, ammonia water or the like into awater-soluble or hydrophilic polymer in which at least a part of thesulfonic acid groups forms a salt. The kind of the cation forconverting, into a salt, the free sulfonic acid group or groups of thesulfonation product polymer is not critical; however, in order to makethe polymer water-soluble, the above-mentioned alkali metal ions,alkaline earth metal ions, ammonium ion and quaternary ammonium ions arepreferred. These cations can be exchanged with other kinds of cations byvarious ion-exchange techniques.

Thus, an aqueous solution of a water-soluble (co)polymer salt isprepared, and in this invention, if necessary, a solid, water-soluble(co)polymer salt can be obtained by separating the (co)polymer salt fromthe aqueous solution and then drying the salt.

The degree of neutralization of the sulfonic acid groups may beappropriately varied within a range in which the (co)polymer salt iswater-soluble or water-dispersible, and the plural sulfonic acid groupsmay form different salts.

The structure of the sulfonation product and the sulfonation productpolymer in this invention can be confirmed from absorption due to thesulfonic acid group indicated in an infrared absorption spectrum of thesulfonation product or its polymer, and the composition ratio of thesulfonation product or its polymer can be determined by a potentiometricor conductometric acid-alkali titration.

Further, the presence of an alkyl group or an olefinic hydrogen can beconfirmed by a nuclear magnetic resonance spectrum, whereby thestructure of the sulfonation product or its polymer can be determined.

The sulfonation product polymer of this invention is a high molecularweight (co)polymer having sulfonic acid groups, which are stronglyacidic, and having a large ion exchange capacity. The sulfonationproduct and the sulfonation product polymer of this invention can beused as a dispersing agent for cement, concrete, calcium carbonate,coal, gypsum, alumina, iron oxide, pigment, a petroleum-coal mixture orthe like; a water-treating agent such as an anti-scaling agent forcalcium carbonate, clacium phosphate, silica or the like or ananti-corrosive; a water-absorbent gel; a reactive emulsifier; asurfactant; a fiber-treating agent; or the like.

The sulfonation product polymer of this invention can further be used inthe form of a homopolymer or a copolymer with other monomers in variousapplications including highly hydrophilic resin, antistatic agent forrubber, improvement of colorability of fiber and the like.

Applications in which the sulfonation product polymer of this inventioncan be used are explained in more detail below.

When the sulfonation product polymer of this invention is used as adispersing agent, the dispersoids to be dispersed therewith are, forexample, solid fuel, cement, dye, pigment, metal oxide and the like. Theabove dispersing agent enables the dispersoid to be stably dispersed andto form a slurry having a low viscosity and excellent fluidity.

The above solid fuel may be any of coal, petroleum coak, pitch, browncoal, sub-bituminous coal, bituminous coal, anthracite and the like, ormay be a de-ashed coal obtained by cleaning them. The kind of coal isnot critical.

The solid fuel may have any particle size as far as it is powdery.Finely divided coal which is now burnt in a thermoelectric power plantcontains at least 70% by weight of 200-mesh pass particles, and thisparticle size indicates a preferable one. However, the dispersing agentconsisting essentially of the sulfonation product or the sulfonationproduct polymer of this invention is not affected by the particle sizeand the kind of the solid fuel, and can exhibit excellent effect on anysolid fuel.

The above dispersing agent may, if necessary, contain a surfactant, anadditive or the like and may be added to a solid fuel composition havinga solid fuel concentration of, preferably 50 to 80% by weight, morepreferably 60 to 75% by weight though this concentration is notcritical.

The larger the amount of the dispersing agent added, the lower theviscosity of the solid fuel composition becomes. Therefore, it ispossible to select an amount of the dispersing agent to be addedcorresponding to any desired viscosity. Usually, the amount may be 0.01to 10% by weight based on the total weight of the composition, and anamount of 0.05 to 1% by weight is preferred in view of workability andeconomical efficiency.

To the solid fuel composition may be, if necessary, added a nonionic oranionic dispersant.

In some cases, a higher stability may be imparted to the solid fuelcomposition by adding thereto a thickening agent, for example, a naturalhigh polymer such as xanthan gum, guar gum or the like; a modifiedcellulose derivative such as carboxymethyl cellulose, hydroxyethylcellulose or the like; or a clay mineral such as montmorillonite,caolin, bentonite or the like.

The additive includes, for example, a chelating agent for trapping thepolyvalent metal contained in the ash component in the solid fuel;potassium polyphosphoric acid; sodium citrate; sodium gluconate;poly(sodium acrylate); polycarboxylic acids; and the like. Also, anantifoaming agent may be added to inhibit the composition from foaming.

In order to prevent the composition from being frozen in winter, theretomay be added a freezing point-depressing agent.

The method of preparing a solid fuel composition is not critical, andthe composition may be prepared by mixing the dispersing agent, thesolid fuel and water in any desired manner. For example, the solid fuelmay be previously pulverized in a dry method and then mixed with anaqueous solution of the dispersing agent; the solid fuel may be formedinto a slurry, to which the dispersing agent is added; or the solidfuel, water and the dispersing agent may be placed in a mill and thenmixed while grinding the solid fuel; or any other method may be used.

In this invention, the cement to be used as the dispersoid includesportland cements such as normal portland cement, rapid-hardeningportalnd cement, super-rapid-hardening portland cement, moderate heatportland cement, sulfate-resisting portland cement, white iron portlandcement and the like; known cements such as blast furnace cement, silicacement, flyash cement, alumina cement, soliditit cement, calciumsilicate or the like; and cement mix prepared by combining two or moreof them, and also includes mixtures of these cements with inorganicmaterials such as gypsum or the like.

The dispersing agent used in this invention serves to disperse thesecements in water, and can be applied to mortar containing sand or gravelor concrete. Also, a cement-compounding agent such as air-entrainingagent, AD-water-reducing agent, quick-setting agent, water-proofingagent, rust-preventive, emulsion for cement or the like may beoptionally added depending upon the purpose of use.

To the cement composition may be added conventional high performancewater-reducing agent, fluidizing agent, for example,naphthalene-sulfonic acid condensate, melamine-sulfonic acid condensate,ligninsulfonic acid or the like.

The amount of the dispersing agent of this invention to be added to thecement composition may be varied depending upon the purpose of use, thekind of cement and the amount of cement, and hence, cannot be determineduniquely. However, the amount is usually 0.002 to 5% by weight,preferably 0.05 to 2% by weight, based on the weight of the cement inorder to obtain a cement composition in which separation of aggregateand bleeding are inhibited.

The amount of water added to cement may be varied depending upon thephysical properties of the hardened cement composition; however, it isusually 20 to 80 parts by weight, preferably 25 to 60 parts by weight,per 100 parts by weight of the cement though this amount is notcritical. The dispersing agent of this invention enables the cement tobe highly dispersed in water regardless of the amount of water.

A cement composition having added thereto the dispersing agent of thisinvention has a very high fluidity, and therefore, is improved very muchin workability, and as compared with cement compositions containingother dispersing agents and having the same fluidity as that of theabove, the former cement composition has a lower water/cement ratio andhence has a higher strength and a smaller amount of cracks.

Accordingly, the cement composition containing the dispersing agent ofthis invention can be used in many applications requiring highworkability and high quality.

The dye and/or pigment to be used as the dispersoid includes basic dyes,acidic dyes, chrome-containing dyes, chrome dyes and disperse dyes suchas di- and triarylmethane dyes, vinylon dye, rhodamine dye, acridinedye, safranine dye, oxazine dye, quinoline dye, thiazole dye, basic azodye, azomethin dye, polymethin dye, azopolymethin dye, basicanthraquinone dye, quinophthalone dye, phthalocyanine dye and the like;inorganic pigments such as ultramarine, cadmium yellow, red iron oxide,chrome yellow, white lead, titanium white, carbon black and the like;and organic pigments such as azo type, triphenylmethane type, quinolinetype, anthraquinone type, phthalocyanine type and the like.

In the case of a dye and/or pigment composition, the dispersing agent ofthis invention can be used, if necessary, together with theabove-mentioned surfactant, additive and the like, and they may be addedto a dye and/or pigment composition having a dye and/or pigmentconcentration of 0.01 to 50% by weight, preferably 0.1 to 40% by weight.

The amount of the dispersing agent may usually be 0.01 to 50% by weightbased on the total weight of the composition, and preferably 0.1 to 30%by weight in view of workability and economical efficiency.

The method of preparing the dye and/or pigment composition is notcritical and comprises mixing the dispersing agent, the dye and/orpigment and water by any desired method.

The dye and/or pigment composition is excellent in dispersibility andwhen it is a basic dye composition, the cation of the water-solublebasic dye is relatively strongly bonded to the anion of the anion typedispersing agent to form a sparingly soluble complex salt, and it doesnot cause ionic dissociation at room temperature as in the case ofconventional basic dye.

Accordingly, the dye and/or pigment composition does not attach to thehuman body and various articles as in the case of commercially availablepowder and liquid of basic dye. Moreover, because of the formation of arelatively stable complex salt, the so-called change with time is verysmall. Also, in the above basic dye composition, the sparinglywater-soluble complex salt formed is finely dispersed therein by thepower of the excessive anionic dispersing agent and is graduallydecomposed with an elevation of the temperature in a dying bath, wherebyonly the basic dye is adsorbed on fiber. Therefore, good uniformdyeability is obtained. In the above basic dye composition, the basicdye tends to form a complex salt, and therefore, it enables compositedyeing with a dye which has generally not been able to be used with thebasic dye, such as an acidic dye, disperse dye or direct dye. Also thecomposition is stable to pH and enables neutral dyeing. Moreover, thedye and/pigment composition containing the dispersing agent of thisinvention has a clear color and a good uniform dyeability.

The metal oxide to be used as the dispersoid includes water-insoluble orsparingly soluble metal oxides of Groups II to VIII, preferably GroupsII, VII and VIII of the Periodic Table. Preferable examples thereof areFeO, Fe₂ O, MnO, ZnO, CoO, NiO, Al₂ O₃, SiO₂, MgO, CaO and the likealone or in admixture. Particularly preferred are ferrites representedby the formula, M'O.Fe₂ O₃ (M' represents a divalent metal, for example,Mn, Fe, Co, Ni, Cu or Zn). Beside the metal oxide, silicon compound suchas silicon nitride, silicon carbide or the like can be appropriatelydispersed using the dispersing agent of this invention.

The particle size of the metal oxide is not critical, though it ispreferably 0.01 to 500 μm, more preferably 0.01 to 30 μm, and mostpreferably 0.1 to 10 μm.

The concentration of the metal oxide in the composition can be increasedby adding the dispersing agent of this invention, and it is usually 50to 90% by weight, preferably 60 to 85% by weight, based on the totalweight of the metal oxide composition.

The amount of the dispersing agent added may be varied depending uponthe kind and particle size of the metal oxide; however, it is preferably0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on theweight of the metal oxide. When the amount is less than 0.01% by weight,the reduction of the viscosity of the composition is not sufficient, andeven if the dispersing agent is added in an amount of more than 10% byweight, the effect of reducing the viscosity is not proportionallyincreased and rather, there is a fear that the molded article obtainedmay be deteriorated in characteristics.

The metal oxide composition comprises, as essential components, theabove dispersing agent, the metal oxide and water and optionally theabove-mentioned surfactant, additive and a third component such asbinder or the like, and can be prepared by adding the metal oxide powderto an aqueous solution of the dispersing agent and stirring theresulting mixture, or adding a small amount of water to the metal oxidepowder to form a cake, then adding an aqueous solution of the dispersingagent and thereafter stirring the resulting mixture.

The metal oxide composition has a lower viscosity than conventionalones, and therefore, it is a slurry having a higher concentration thanconventional ones, in spite of which the characteristics of the finalmolded article, for example, magnetic properties in the case of ferrite,are not deteriorated. The metal oxide composition is compatible with anadditive such as a binder or the like, and hence, has a good packingproperty when it is press-molded. Therefore, when the metal oxidecomposition is a slurry of a ceramic raw material such as alumina or thelike, the composition can be subjected as such or after the necessarytreatment, to molding and sintering, and the resulting product can beappropriately used in the formation of a core of magnet or theproduction of magnetic tape.

A water-treating agent comprising the sulfonation product and/or thesulfonation product polymer of this invention as an effective componentcan be added at one time, intermittently or continuously to the objectwater system. The amount of the water-treating agent added may be varieddepending upon the water system, and an amount of 0.1 to 100 ppm,preferably 1 to 50 ppm, is sufficient to exhibit an anti-scaling effect.

The anti-scaling effect of the above water-treating agent is exhibitedagainst potassium phosphate scale, calcium carbonate scale, zincphosphate scale, zinc phosphonate scale and the like.

The above water-treating agent is also effective as a cleaner forpiping, a slime-accumulation-preventing agent or a high polymercoagulant and also as a treating agent for living waste water andindustrial waste water in pulp industry, iron industry and the like.

When the above water-treating agent is used, it can be combined with aconventional water-treating agent (anti-scaling agent), ananti-corrosive, an alkali reagent, a slime-accumulation-preventingagent, a sterilizing agent or the like.

The above conventional water-treating agent includes polyacrylic acidsalt, partially hydrolyzed polyacrylamide, maleic acid polymer, itaconicacid polymer, hydroxyethyl methacrylate-containing acrylic acidcopolymer and the like, and the anti-corrosive includeshydroxycarboxylic acids, thiazoles, triazoles, amines, hydroxamic acidsand the like.

The slime-accumulation-preventing agent includes chlorinating agentssuch as chlorine gas, calcium hypochlorite, sodium hypochlorite, sodiumchloroisocyanurate and the like; quaternary ammonium salts; brominatingagents; organic nitrogen-sulfur reagents and the like.

The above water-treating agent comprising the sulfonation product or thesulfonation product polymer is characterized by being free fromphosphorus compound; however, may be blended, if necessary, with aphosphoric acid type water-treating agent such as a phosphoric acidsalt, a phosphonic acid salt or the like; and an anti-corrosive.

When the sulfonation product or the sulfonation product polymer of thisinvention is used, there is obtained a anti-scaling agent which canprevent metal ions from being deposited even when the metal ionconcentration is high and which is free from phosphoric compound.

The fiber-treating agent comprising the sulfonation product and/or thesulfonation product polymer as an effective component can be used in theform of an aqueous solution or an aqueous emulsion.

It is also possible to improve the hydrophylic property, antistaticproperty and dyeability of fiber by copolymerizing a small amount of thesulfonation product of this invention on the fiber.

The amount of the fiber-treating agent added may be varied dependingupon the kind of the fiber to be treated though it is usually 0.01 to10% by weight, preferably 0.05 to 3% by weight, based on the weight ofthe fiber.

When the above fiber-treating agent is used, there may be added thereto,if necessary, a conventional additive, for example, textile auxiliary,detergent, dyeing assistant, finishing auxiliary, bleaching agent or thelike.

The fiber to be treated with the above fiber-treating agent includessynthetic fibers such as polyester fiber, nylon fiber, polypropylenefiber, acrylic fiber, aramide fiber, carbon fiber and the like andnatural fibers such as silk, cotton, flax, wool and the like.

The above fiber-treating agent is excellent in enhancement ofspinnability, strechability, antistatic property, hygroscopicity,dyeability, detergability and the like of fiber, and therefore, can bewidely used as auxiliaries in spinning or stretching step, as apre-treating agent in antistatic treatment or hydroscopicity-impartingtreatment and as a detergent for raw wool.

The above plating bath additive composition comprising the sulfonationproduct and/or the sulfonation product polymer of this invention as aneffective component can be applied to various plating baths. The amountof the additive composition added to the plating bath may be varieddepending upon the kind of plating bath, though it is usually 0.1 to 100g/liter, preferably 1 to 30 g/liter, of the plating bath. When it isless than 0.01 g/liter, the effect of the additive composition is notobtained, and even if the additive composition is used in an amountlarger than 30 g/liter, the effect of the additive composition is notproportionally increased. Hence, such a large amount is economicallydisadvantageous. In addition, in such a large amount, the gloss ofsurface of the plated article becomes uneven.

The plating bath to which the above additive composition for platingbath can be applied includes known plating baths such as copper platingbath, nickel plating bath, chromium plating bath, zinc plating bath,cadmium plating bath, tin plating bath, gold plating bath, silverplating bath, brass plating bath, bronze plating bath, tin-lead alloyplating bath, tin-nickel alloy plating bath and the like.

When the additive composition for plating bath is used, thereto may beadded, if necessary, known additives such as formaline, glue, phenol,ethanolamine, heliotropin, cresolsulfonic acid, vinylsulfonic acid,allylsulfonic acid, methacrylsulfonic acid, styrenesulfonic acid,2-acrylamidopropanesulfonic acid, grape suger and the like.

The plating bath having added thereto the above additive composition canbe used under the following conditions, for example:

    ______________________________________                                        Anodic current density:                                                                             0.5-90 A/dm.sup.2                                       Bath voltage:         0.5-20 V                                                Bath temperature:     1.5-80° C.                                       ______________________________________                                    

The above plating bath additive composition is excellent in enhancementof gloss of plated surface, uniformity of gloss, uniform deposition,surface smoothness and extendability of plated layer, and hence, can bewidely used in plating a metal surface and plating a resin such as ABSresin, polycarbonate, phenol resin, polypropylene, nylon, fluororesin,polyvinyl chloride, polyacetal, polyethylene, polyphenylene oxide andthe like.

The above plating bath additive composition makes it possible to obtaina very uniform gloss, a good surface smoothness, a uniformelectrodepositability in a wide range of bath temperature and a widerange of anodic current density and to plate articles at a high speed.

The sulfonation product and/or the sulfonation product polymer of thisinvention prepared in the form of a solution can be used as it is inpreparing an excavation-muddy water or may be dried and thenappropriately pulverized prior to the use. In the latter case, thesulfonation product and/or the sulfonation product polymer is used inthe form of powder or particles. Such powder or particles are easilydissolved in water.

The amount of the excavation-muddy water-treating agent used ispreferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight,based on the weight of the muddy water.

When using the above excavation-muddy water-viscosity-adjusting agent,thereto may be added, if necessary, conventional additives, for example,dispersing agents such as polyphosphoric acids, ligninsulfonic acids,nitrohumic acids, phosphonic acids, polycarboxylic acids and the like;water-soluble high molecular weight compounds such as carboxymethylcellulose, starch derivatives and the like; surfactants; pH-adjustingagents such as soda ash and the like; muddy water-leakage preventingagents such as press remainders of cotton seed and the like; etc. insuch an amount that the excellent effect of the muddy water-treatingagent is not diminished.

The excavation-muddy water-viscosity-adjusting agent can be applied tomuddy water consisting essentially of a bentonite suspension or abentonite suspension containing at least one member selected fromatapalgait, asbestos and sepiolite. The base for the muddy water may benot only clear water, but also sea water or water containing a largeamount of salts such as calcium chloride and the like.

The above excavation-muddy water-viscosity-adjusting agent exhibitsexcellent heat resistance and salt resistance. In particular, it has anexcellent effect on muddy water such as that containing a large amountof various ions, for example, sea water-based muddy water or thatcontaining cement component.

A water-absorbent crosslinked product can be obtained by crosslinking atleast one member selected from (a) the sulfonation product of thisinvention, (b) the polymer of the sulfonation product of this inventionand (c) the copolymer of the sulfonation product with other monomercopolymerizable therewith. In this crosslinking, an alkenyl monomerand/or a crosslinking monomer may be used in combination therewith.

The alkenyl monomer includes (meth)acrylic acid; (meth)acrylic acidderivatives such as alkali metal salts of (meth)acrylic acid, ammonium(meth)acrylate, (meth)acrylamide, N,N-dimethyl (meth)acrylamide,2-hydroxydiethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylamide,2-hydroxypropyl (meth)acrylamide, polyethylene glycol mono(meth)acrylateand the like; 2-vinylpyridine; 4-vinylpyridine; vinyl acetate; vinylformate; styrene; acrylonitrile; N,N-dimethylaminopropylacrylamide;N-methylolacrylamide; (meth)allyl acetate; glycidyl (meth)acrylate;acrolein; allyl alcohol; vinylmethyl ethyl ketone; vinyl methyl ether;2-acrylamido-2-methylpropanesulfonic acid; p-vinylstyrenesulfonic acid(or its salt); vinyltoluenesulfonic acid (or its salt); and the like.(Meth)acrylic acid, its salts and derivatives are preferred, and may beused alone or in combination of two or more.

The above alkenyl monomers may be used in such an amount that theperformance of the above water-absorbent crosslinked product is notdiminished. The amount of the alkenyl monomer used is usually not morethan 98% by weight, preferably not more than 95% by weight, morepreferably not more than 90% by weight, based on the total weight of the(a) to (c) components and the alkenyl monomer.

The crosslinking monomer includes ethylene glycol di(meth)acrylate,diethylene glycol di(meth)acrylate, polyethylene glycoldi(meth)acrylate, propylene glycol di(meth)acrylate, polypropyleneglycol di(meth)acrylate, glycerine (meth)acrylate, N,N-methylenebis(meth)acrylamide, diallyl phthalate, diallyl fumarate, diallylterephthalate, triallyl cyanurate, triallyl isocyanurate, triallylphosphate and the like, and these may be used alone or in combination oftwo or more.

The amount of the crosslinking monomer used may be varied depending uponthe water-absorbency, gel strength and the like of the water-absorbentcrosslinking product obtained. Usually, it is not more than 10% byweight based on the total weight of the components (a) to (c) and thealkenyl monomer. In view of the gel strength, it is preferably 0.001 to5% by weight, more preferably 0.002 to 2% by weight, and most preferably0.005 to 0.5% by weight, based on the total weight of the components (a)to (c) and the alkenyl monomer. When the amount exceeds 10% by weight,the water-absorbency is reduced.

The total amount of the (a) to (c) components contained in the abovewater-absorbent crosslinked product is at least 2% by weight, preferably3 to 70% by weight, more preferably 5 to 50% by weight, and when theamount is less than 2% by weight, the effect of the sulfonation productand/or the sulfonation product polymer of this invention cannot beobtained.

The water-absorbent crosslinked product can be obtained by subjecting tocrosslinking at least one of the (a) to (c) components, and optionallythe alkenyl monomer and/or the crosslinking monomer by the followingmethods (1) to (5):

(1) At least one of the (a) to (c) components, the alkenyl monomer andthe crosslinking monomer are subjected to polymerization andcrosslinking with a crosslinking agent.

(2) At least one of the (a) to (c) components and the crosslinkingmonomer are subjected to polymerization and crosslinking with acrosslinking agent.

(3) At least one of the (a) to (c) components and the alkenyl monomerare subjected to polymerization and crosslinking with a crosslinkingagent.

(4) At least one of the (a) to (c) components is subjected tocrosslinking with a crosslinking agent.

(5) At least one of the (a) to (6) components is heated in the absenceof a crosslinking agent to crosslink the same.

Among these crosslinking methods, the methods (1) to (4) are preferableand the methods (1) to (3) are more preferable. The method (1) is themost preferable one.

Of the above (a) to (c) components, preferred are the components (b) and(c).

The above-mentioned crosslinking agent may be any of the conventionalones, and preferably, it is sulfur, an inorganic sulfur compound, anorganic sulfur compound or a radical generator.

Particularly, when the alkenyl monomer and the crosslinking monomer arepresent as in the methods (1) to (3), it is preferable to use a radicalgenerator, particularly a water-soluble radical generator.

The radial generator includes those which are used in the(co)polymerization of the above (b) and (c) components, and the amountof the radical generator used is usually 0.01 to 10% by weight,preferably 0.1 to 2% by weight, based on the total weight of the (a) to(c) components and the alkenyl monomer and/or the crosslinking monomerwhich are optionally used.

In the crosslinking of at least one of the (a) to (c) components in thepresence of the alkenyl monomer and/or the crosslinking monomer whichare optionally used, a solvent is not necessarily used though it ispreferable to effect the crosslinking in the presence of a solvent. Thissolvent includes the organic solvents used in the above-mentioned(co)polymerization of at least one of the (b) to (c) components.

In the above crosslinking, there may also be used a solvent-crosslinkingmethod in which water is used as a solvent or a reversed phasesuspension crosslinking (polymerizing) method in which a stablewater-in-oil type suspension is formed using, for example, asorbitane-fatty acid ester as a dispersing agent.

The crosslinking temperature is usually 0° to 150° C., preferably 5° to100° C. and the crosslinking time is usually 0.5 to 48 hours.

In the above crosslinking, the method of adding the (a) to (c)components and the alkenyl monomer and/or the crosslinking monomer isnot critical, and they may be added at one time, continuously or inportions.

The above water-absorbent crosslinked product can be changed from itsacid form to form of an alkali metal salt, an alkaline earth metal salt,an ammonium salt or a quaternary ammonium salt or from its salt form toacid form or from its salt form to another salt form by an ion exchangemethod or by neutralization.

The above water-absorbent crosslinked product can be blended with anappropriate amount of an elastomer to form an elastomer compositionhaving excellent performance as a water-absorbent or hydrophilicelastomer.

The above water-absorbent crosslinked product can be blended with anappropriate amount of a synthetic resin such as a thermoplastic resin ora thermosetting resin to form a resin composition having excellentwater-absorbency and hydrophilic property.

The mixing ratio of the water-absorbent crosslinked product to theelastomer or the synthetic resin is not critical, and they may beblended in such an appropriate proportion that the desired purpose canbe achieved. The former/the latter ratio (by weight) is usually 1/99 to99/1, preferably 2/98 to 90/10, more preferably 5/95 to 80/20, and mostpreferably 7/93 to 50/50.

In particular, the water-absorbent crosslinked product has double bondsin its molecule, and therefore, can be co-crosslinked with variouselastomers having unsaturations such as natural rubber,styrene-butadiene rubber, polybutadiene rubber, acrylonitrile-butadienerubber, chloroprene rubber, butylene rubber, ethylenepropylene-dienerubber, unsaturated acrylic rubber and the like.

The method of blending the water-absorbent crosslinked product with theelastomer may be either a method in which the two are fed simultaneouslyto a mixer and kneaded therein or a method in which an additive ispreviously added to one of the two and then the other is blended withthe resulting mixture.

The mixing may be conducted by means of an extruder, a Banbury mixer, akneader, a roll or the like at a temperature of 80° to 250° C.,preferably 100° to 200° C. for a period of 0.1 to 2 hours, preferably0.2 to 1 hour. Preferably, an internal mixer such as Banbury mixer,kneader or the like is used.

The composition comprising the water-absorbent crosslinked product andthe elastomer or the synthetic resin may further contain conventionallyused compounding agents, for example, fillers, dispersing aids,plasticizers, softening agents, heat-resistives, coloring agents,ultraviolet absorbers, flame retardants, oil-resistance-improvingagents, foaming agents, anti-scorching agents, tackifiers, lubricantsand the like depending upon the purpose.

The above composition can be subjected to molding and vulcanizationunder conventional rubber-producing conditions after being compoundedwith a crosslinking agent, for example, an organic hydroperoxide, acrosslinking co-agent, polyol type vulcanizing agent, vulcanizationaccelerator, amine type vulcanizing agent or the like by means of aconventional mixer such as roll, Banbury mixer or the like.

The above organic peroxide includes those mentioned as to the productionof the water-absorbent crosslinked product.

The amount of the crosslinking agent is preferably 0.1 to 10 parts byweight, more preferably 0.5 to 7 parts by weight, per 100 parts byweight of the composition.

The amount of the polyol type vulcanizing agent added is usually 0.1 to20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts byweight of the composition.

The amount of the vulcanization accelerator added is usually 0.2 to 10parts by weight per 100 parts by weight of the composition.

The amount of the amine type vulcanizing agent added is usually 0.1 to10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 partsby weight of the composition.

The vulcanization of the above composition is usually effected bysubjecting it to primary vulcanization at a temperature of 80° to 200°C. for a period of several minutes to 3 hours at a pressure of 20 to 200kg/cm² and then, if necessary, to secondary vulcanization at atemperature of 80° to 200° C. for a period of 1 to 4 hours, whereby acrosslinked product can be obtained.

The water-absorbent crosslinked product can be used in sanitaryapplications such as paper diapers, sanitary napkins, materials forincontinence of urine, materials for treating pet excreta and the like;agricultural and horticultural applications such as soil water-holdingagents, soil conditioners and the like; civil engineering applicationssuch as sealing materials, muddy water-leakage-preventing materials,packing materials, muddy water-solidifying agents and the like; andconstruction applications such as water-absorbing agents for concrete,cement or the like, reinforcing agents, water-absorbent hygroscopicsheetings, wall materials for preventing dew condensation,water-absorbent laminates and the like.

In the composition comprising the water-absorbent crosslinked productand the elastomer or the synthetic resin, the strength of thewater-absorbent crosslinked product is increased by the action of thelatter components, and the water-absorbent crosslinked product impartshydrophilic property, water-absorbency or oil resistance to theelastomer or the synthetic resin, and hence, the composition can be usedin such applications that such characteristics can be effectivelyexhibited.

The sulfonation product can be used as a reactive emulsifier and thesulfonation product polymer can be used as surfactant or emulsifier.

This invention is described in more detail below referring to Examples.However, it should not be construed that this invention is restricted tothese Examples.

EXAMPLES

In the Examples, % and parts are by weight unless otherwise specified.

Example 1

400 ml of dehydrated and deoxygenated methylene chloride was placed in a1-liter, four-necked flask purged with nitrogen. Thereto was added 31 mlof dehydrated and deoxygenated dioxane. The mixture was cooled to 5°-10°C. with stirring.

Thereinto was dropped 15 ml (28.8 g=0.36 mole) of sulfur trioxide toform a complex of sulfur trioxide with dioxane. The reaction wascontinued for a further 15 minutes.

Into the reaction mixture was dropped 150 ml of a methylene chloridesolution containing 24.5 g (0.36 mole) of isoprene(2-methyl-1,3-butadiene), in 1 hour. After the completion of thedropping, stirring was continued for a further 30 minutes.

To the resulting mixture was added 100 ml of an aqueous solutioncontaining 14.4 g of sodium hydroxide (concentration: about 14%). Theflask inside was made vacuum. The flask was slowly heated to 40° C. in awater bath, the solvent and dioxane were removed by distillation and theresidue was dried, whereby 50.2 g of a product (crude sodium2-methyl-1,3-butadiene-1-sulfonate) was obtained.

The product was dissolved in 300 ml of water, and 200 ml of toluene wasadded thereto. The mixture was shaked vigorously to extract atoluene-soluble portion. The aqueous layer was separated and dried.

2 g of the thus obtained sodium 2-methyl-1,3-butadiene-1-sulfonate(hereinafter referred to as MBSN) was placed in a 30-ml pressure bottle,and the bottle was purged with nitrogen. Thereto was added 0.06 g ofsodium persulfate. The pressure bottle was fixed to a rotary polymerizerof 70° C. and polymerization was effected for 2 hours.

The polymerization-conversion was 65%. A gel permeation chromatographyshowed that the obtained polyisoprene had a sodiumpolystyrenesulfonate-reduced weight-average molecular weight(hereinafter referred to as weight-average molecular weight) of 20,000.The amount of the sulfonic acid group of the polymer was found to be 5.5milliequivalents/g by the titration of the group.

The NMR spectrum (¹ H-NMR) and IR absorption spectrum of the abovepolymer are shown in FIGS. 1 and 2, respectively. It was found fromFIGS. 1 and 2 that the polymer of this Example had the followingstructural unit as an essential unit. ##STR7## In the above formula, mand n each represent the number of the structural unit corresponding tothe weight-average molecular weight of the polymer, and the ratio of m:nwas found from the NMR spectrum to be about 54:46.

Example 2

The MBSN synthesized in Example 1 and methacrylic acid were subjected tocopolymerization according to the following procedure:

13 g (0.076 mole) of the MBSN and 6.5 g (0.076 mole) of methacrylic acidwere placed in a 100-ml pressure bottle. 58.5 g of water and 0.20 g ofpotassium persulfate were added. The pressure bottle was then stopperedand the contents were subjected to polymerization for 5 hours at 70° C.

The polymerization conversion was 74%. The resulting polymer had aweight-average molecular weight of 28,500.

The polymer was subjected to dialysis with a cellulose tube to removethe low-molecular weight portion and then measured for NMR spectrum (¹H-NMR) and IR absorption spectrum. The spectra are shown in FIGS. 3 and4, respectively.

The proportion of the two monomers in the copolymer was determined fromthe NMR spectrum of FIG. 3, to find that the MBSN/methacrylic acid molarratio was 29/71.

Examples 3 to 5

The same procedure as in Example 2 was repeated, except that themethacrylic acid used in Example 2 was replaced by acrylic acid,acrylamide or sodium styrenesulfonate (NaSS). The results obtained areshown in Table 1.

Each of the polymers obtained was measured for NMR spectrum (¹ H-NMR)and IR absorption spectrum. The two spectra of each polymer showed theabsorption of a copolymer of a sulfonation product (MBSN) with anothermonomer.

Shown in FIG. 5 are GPC (gel permeation chromatography) charts of theMBSN homopolymer of Example 1 and the MBSN/NaSS copolymer of Example 5.

As is clear from FIG. 5, the MBSN homopolymer of Example 1 can bedetected by the detector of refractive index (RI) but cannot be detectedby the detector of UV absorption spectrum (UV, wavelength=254 nm).

Meanwhile, the MBSN/NaSS copolymer of Example 5 can be detected by RIand UV, and RI and UV have similar shapes.

If the polymer of Example 5 is a mixture of a MBSN homopolymer with aNaSS homopolymer, the MBSN homopolymer is not detected by a UV detectorand only the NaSS homopolymer is detected and the RI and the UV giveentirely different shapes. Actually, however, the GPC chart of thepolymer of Example 5 gives similar shapes in RI and UV, and thisindicates that the polymer of Example 5 is a copolymer.

Comparative Example 1

The same procedure as in Example 1 was repeated, except thatcommercially available sodium vinylsulfonate was used in place of theMBSN.

The polymerization conversion was 32% and the polymer obtained had aweight-average molecular weight of about 1,000.

Comparative Example 2

The same procedure as in Example 1 was repeated, except thatcommercially available sodium allylsulfonate was used in place of theMBSN.

The polymerization conversion was 47% and the polymer obtained had aweight-average molecular weight of about 400.

As is clear from the comparison between Example 1 and ComparativeExamples 1 and 2, the monomer (sulfonation product) used in thisinvention gives a high conversion and a polymer of high molecular weightand accordingly is an industrial raw material superior to known sodiumvinylsulfonate and sodium allylsulfonate.

                                      TABLE 1                                     __________________________________________________________________________                                                Comparative                                                                          Comparative                             Example 1                                                                           Example 2                                                                            Example 3                                                                           Example 4                                                                           Example 5                                                                           Example 1                                                                            Example                    __________________________________________________________________________                                                       2                          MBSN (mole)  0.008 0.076  0.076 0.076 0.076 --     --                         Other monomer                                                                 type         --    Methacrylic                                                                          Acrylic                                                                             Acrylamide                                                                          Sodium                                                                              Sodium Sodium                                        acid   acid        styrene-                                                                            vinyl- allyl-                                                           sulfonate                                                                           sulfonate                                                                            sulfonate                  (mole)       --    0.076  0.076 0.076 0.076 0.008  0.008                      Radical initiator (parts)                                                                  3     1      1     1     1     3      3                          Solvent/monomer                                                                            4     3      3     3     3     4      4                          (weight ratio)                                                                Polymerization                                                                             65    74     67    61    76    32     47                         conversion (%)                                                                Weight-average molecular                                                                   20,000                                                                              28,500 26,000                                                                              38,000                                                                              ≧50,000                                                                      About 1,000                                                                          About 400                  weight                                                                        Mole ratio of components                                                                   100/0 29/71  60/40 74/26 45/55 0/100  0/100                      in polymer (MBSN/other                                                        monomer)                                                                      NMR spectrum FIG. 1                                                                              FIG. 3 --    --    --    --      --                        IR absorption spectrum                                                                     FIG. 2                                                                              FIG. 4 --    --    --    --     --                         __________________________________________________________________________

Example 6

The same procedure as in Example 1 was repeated, except that 400 ml ofdioxane was used in place of the 400 ml of methylene chloride and thereaction was conducted at 20° C., to form a complex of sulfur trioxidewith dioxane.

Into the reaction mixture was dropped 150 ml of a dioxane solutioncontaining 24.5 g (0.36 mole) of isoprene in 1 hour. After thecompletion of the dropping, stirring was continued for a further 30minutes.

Thereinto was then dropped a hexane solution containing 1.6 moles/literof n-butyllithium in 30 minutes. The mixture was subjected to reactionfor a further 12 hours at 30° C.

After the completion of the reaction, 300 ml of methanol was added tothe reaction mixture. The solvent was removed and the residue was driedto obtain 45.1 g of a product (lithium2-methyl-1,3-butadiene-1-sulfonate).

The product was subjected to polymerization in the same manner as inExample 1. The polymerization conversion was 9.8%. GPC indicated thatthe obtained polymer had a weight-average molecular weight of 9,000.

Example 7

The same procedure as in Example 1 was repeated, except that a 50%aqueous sodium hydroxide solution was used and, after the feeding ofthis solution, stirring was continued for 5 hours at 40° C. Theresulting precipitate was collected by filtration and vacuum-dried toobtain 62.5 g of a colorless powder.

This sulfonation product was measured for NMR spectrum (¹ H-NMR and ¹³C-NMR), IR absorption spectrum and GPC, whereby the formation of theproduct was confirmed in the same manner as in Example 1.

The sulfonation product was subjected to the same polymerization as inExample 1. The polymerization conversion was 71% and the polymerobtained had a weight-average molecular weight of 41,000.

Example 8

An aqueous sodium hydroxide solution was fed to a reactor in the samemanner as in Example 7. The water in the reaction system wasazeotropically removed with methylene chloride and, after cooling, onlymethylene chloride was returned to the reaction system. When thisprocedure was repeated for 24 hours, the amount of water taken out ofthe reaction system became constant.

The resulting precipitate was vacuum-dried to obtain 65.7 g of acolorless powder.

The powder was subjected to polymerization in the same manner as inExample 1 to obtain a polymer having a weight-average molecular weightof 40,000 at a polymerization conversion of 75%.

Comparative Example 3

The same procedure as in Example 1 was repeated, except that 500 ml ofdistilled water was added in place of the aqueous sodium hydroxidesolution; the resulting mixture was stirred for 5 hours at 40° C.; thesystem was heated at a reduced pressure of 600 mm Hg to remove theorganic solvent completely and effect concentration until 200 g of anaqueous solution was obtained. The solids content in the aqueoussolution was 22.6%. To the solution was added 3 parts of potassiumpersulfate per 100 parts of the solids and the mixture was subjected topolymerization in the same manner as in Example 1. However, no polymerwas obtained.

This is presumed to be because, when water was used alone,2-methyl-4-hydroxy-2-butene-1-sulfonic acid was formed and no intendedsulfonation product of conjugated diene was obtained as described inIzuvest. Akad. Nauk. SSSR, Ser, Khim. 1327 (1979).

Application Example 1 and Comparative Application Example 1

The copolymers to be used in Application Example 1, Run Nos. 1-5 wereproduced in the same manner as in Example 2.

As coal, there was used a coal produced in China, containing 76% of 200mesh-pass particles, 6.5% of ash and 1.6% of sulfur. 0.6%, based on thecoal, of a dispersing agent shown in Table 2 was previously added towater. Thereto was slowly added a given amount of particles of the coal.The mixture was stirred for 15 minutes at 3,000 rpm by a homomixer toprepare 5 coal slurries of 70% concentration.

Each of the coal slurryies thus obtained was measured for viscosity at25° C. The results are shown in Table 2.

For comparison, results of the use of no dispersing agent (Run No. 6),the use of a condensation product of naphthalenesulfonic acid (Run No.7) and the use of a nonionic surfactant of polyethylene oxide type (RunNo. 8) are also shown in Table 2 as Comparative Application Example 1.

As is clear from Table 2, the coal slurry compositions using thedispersants of this invention are superior.

                                      TABLE 2                                     __________________________________________________________________________           Monomer composition                                                           used in Production of                                                                           Weight-average                                                                        Amount of                                           Copolymer (dispersant)                                                                          molecular                                                                             dispersing                                                                             Slurry                                     (mole ratio)      weight of                                                                             agent added                                                                            viscosity                                  MBSN                                                                              Copolymerizable monomer                                                                     copolymer                                                                             (% based on coal)                                                                      (cP)                                __________________________________________________________________________    Application                                                                   Example 1                                                                     Run No. 1                                                                            1   1   Polyethylene                                                                            28,500  0.6      1,070                                              glycol                                                                        methacrylate                                                   Run No. 2                                                                            1   0.5 Polyethylene                                                                            25,000  0.6      1,210                                              glycol                                                                        acrylate                                                        Run No. 3                                                                            1   1   Sodium styrene-                                                                         43,000  0.6        890                                             sulfonate                                                      Run No. 4                                                                            1   1   (Acrylonitrile)                                                                         23,000  0.6        920                               Run No. 5                                                                            1   1   (Isoprene)                                                                               9,500  0.6      1,010                               Comparative                                                                   Application                                                                   Example 1                                                                     Run No. 6                                                                            No dispersing agent                                                                             --      0        No slurry                                                                     formed                              Run No. 7                                                                            Condensation product of                                                                         --      0.6      1,570                                      naphthalenesulfonic acid                                               Run No. 8                                                                            Nonionic sulfactant of                                                                          --      0.6      1,650                                      polyethylene oxide type                                                       (HLB: 16.3)                                                            __________________________________________________________________________

Application Example 2 and Comparative Application Example 2

In a 25-liter forced milling mixer were placed 7.91 kg of a fineaggregate (a river sand of 0-5 mm in diameter produced from Utsuberiver, Mie Prefecture, Japan), 9.74 kg of a coarse aggregate (a riversand produced from the same river, weight ratio of 5-10-mm diameterportion to 10-15-mm diameter portion to 15-20-mm diameterportion=3:4:3), 3.20 kg of a normal portland cement [a 1:1:1 (by weight)mixture of an Asano Cement product, a Mitsubishi Cement product and anONODA CEMENT product], 1.75 kg of water and 0.48 kg of an air-entrainingagent (pinsole). They were kneaded for 3.5 minutes to obtain a freshconcrete. The concrete was measured for slump and an amount of airentrained, which were 8.0 cm and 4.3%, respectively.

After 15 minutes, to the above concrete was added a 40% aqueous solutionof the copolymer obtained in Application Example 1, Run No. 3 or 4 or ofthe polymer obtained in Example 1; then the mixture was stirred for 30seconds and measured for slump. By repeating this procedure, there weredetermined the amount of the dispersing agent (polymer or copolymer)added and the amount of air entrained when the slump became 18 cm±1 cm.The results are shown in Table 3. In Comparative Application Example 2,there were used, as a dispersing agent, a condensation product of sodiumnaphthalenesulfonate (a commercial product) (Run No. 4) and acondensation product of sodium melaminesulfonate (a commercial product)(Run No. 5). These results are also shown in Table 3.

As is clear from Table 3, as compared with commercially availablefluidizing agents, the dispersants of this invention can give highfluidity to concrete in a small addition amount.

The above fresh concrete and fluidized concretes were subjected tostandard curing and then measured for compression strength after 28 daysof age according to JIS A 1108. The results are shown in Table 3. Ascompared with the compression strength (375-385 kg/cm²) of the freshconcrete having a slump of 8 cm, the concretes containing the dispersingagents of this invention were fluidized to a slump of 18±1 cm;nevertheless have substantially the same compression strength as that ofthe fresh concrete.

                                      TABLE 3                                     __________________________________________________________________________           Monomer composition                                                           charged in production of                                                                       Amount of                                                    copolymer (dispersant)                                                                         dispersing Amount of                                         (mole ratio)     agent added                                                                              air   Compression                                     Copolymerizable                                                                            (% based on                                                                          Slump                                                                             entrained                                                                           strength                                    MBSN                                                                              monomer      cement)                                                                              (cm)                                                                              (%)   (kg/cm.sup.2)                        __________________________________________________________________________    Application                                                                   Example 2                                                                     Run No. 1                                                                            1   0.4 Sodium   0.35   18.1                                                                              4.7   385                                                 styrene-                                                                      sulfonate                                                      Run No. 2                                                                            1   0.2 (acrylonitrile)                                                                        0.40   18.3                                                                              3.5   375                                  Run No. 3                                                                            1         --     0.43   18.3                                                                              3.9   380                                  Comparative                                                                   Application                                                                   Example 2                                                                     Run No. 4                                                                            Condensation product of                                                                        0.58   17.8                                                                              4.8   360                                         sodium naphthalene-                                                           sulfonate                                                              Run No. 5                                                                            Condensation product of                                                                        1.37   18.1                                                                              4.5   355                                         sodium melaminesulfonate                                               __________________________________________________________________________

Application Example 3 and Comparative Application Example 3

100 parts of α-semihydrate (containing a solidification retarder) wasmixed with 30 parts of water and a dispersant shown in Table 4 in anamount shown in Table 4. The mixture was stirred for 30 seconds andimmediately measured for dispersibility (flow value and viscosity) andamount of water bled. The results are shown in Table 4.

The flow value was obtained by placing a cylinder of 40 mm in diameterand 90 ml in internal volume on a glass plate, pouring a gypsum slurryinto the cylinder, pulling the cylinder upward and measuring the spreadof the gypsum slurry on the glass plate.

The viscosity was measured using a BL type viscometer (rotor No. 3, 60rpm).

The amount of water bled was obtained by placing 100 ml of a gypsumslurry in a 200-ml graduated cylinder of 25 mm in diameter, allowing theslurry to stand for 1 hour and then measuring the amount of the waterbled on the slurry surface.

                                      TABLE 4                                     __________________________________________________________________________           Monomer composition                                                                           Amount of                                                     charged in production of                                                                      dispersing                                                                           Dispersibility                                                                         Amount of                                     copolymer (mole ratio)                                                                        agent added                                                                          Flow     water                                             Copolymerizable                                                                           (% based on                                                                          value                                                                             Viscosity                                                                          bled                                          MBSN                                                                              monomer     gypsum)                                                                              (mm)                                                                              (cP) (ml)                                   __________________________________________________________________________    Application                                                                          1   1 (Methacrylic acid)                                                                      0.75   215   850                                                                              0.8                                    Example 3                                                                     Comparative                                                                          Calcium ligninsulfonate                                                                       0.75   160 2,050                                                                              4.3                                    Application                                                                   Example 3                                                                     __________________________________________________________________________

Application Example 4

40 parts of a basic yellow dye, C. I. Basic Yellow 11 (C. I. No. 48055)was added to 400 parts of water, and they were stirred thoroughly.

Thereto was slowly added 60 parts of the dispersing agent used inApplication Example 1, Run No. 1, whereby a sparlingly soluble dyecomplex was formed. The complex became a fine dispersion gradually. Ithad a commercial value as a liquid dye. When the fine dispersion wasdried according to a known conventional technique, for example, spraydrying, it was possible to obtain 100 parts of a dispersion of the aboveyellow dye. The same thing could be applied to other dispersants used inApplication Example 1.

The formation of a fine dispersion of a dye complex became easier by aconventional mixing technique such as the use of a colloid mill or thestirring of the fine dispersion in the presence of sand.

Application Example 5 and Comparative Application Example 4

In a 300-ml erlenmeyer flask were placed distilled water, an aqueousanti-scaling agent (a water-treating agent) solution, an aqueous sodiumorthophosphate dodecahydrate solution, an aqueous calcium chloridedihydrate solution and an aqueous sodium hydrogen-carbonate solution sothat the resulting mixture had a total amount of 200 g and contained 5(or 3) ppm of the anti-scaling agent, 10 ppm of phosphate ion (PO₄ ³⁻),100 ppm of calcium ion (Ca2⁺) and 100 ppm of carbonate ion (CO₃ ²⁻).Then, the flask was placed in a constant temperature bath of 60° C. andheated for 15 hours to promote the generation of scale.

The flask was cooled at room temperature, and the flask contents werefiltered through a 0.45 μm membrane filter. The filtrate was subjectedto quantitative analysis of phosphorus ion according to the molybdenumblue reaction specified by JIS K 0101. The results are shown in Table 5.

In Comparative Application Example 4, similar tests were conducted usingno anti-scaling agent (Run No. 6) and a polyacrylic acid (Run No. 7).These results are shown also in Table 5.

The MBSN used in the synthesis of copolymer (water-treating agent) wasthe same as used in Example 1, and each copolymer used was produced inthe same manner as in Example 2.

                                      TABLE 5                                     __________________________________________________________________________           Monomer composition                                                           charged in production of                                                                      Weight-            Concentration                              copolymer       average                                                                             Amount of                                                                            Cloudiness                                                                          of                                         (mole ratio)    molecular                                                                           anti-scaling                                                                         of aqueous                                                                          phosphate                                      Copolymerizable                                                                           weight of                                                                           agent added                                                                          solution                                                                            ion                                        MBSN                                                                              monomer     copolymer                                                                           (ppm)  after test                                                                          (ppm)                               __________________________________________________________________________    Application                                                                   Example 5                                                                     Run No. 1                                                                            1   1 (Methacrylic acid)                                                                      5,000 5      No    9.7                                 Run No. 2                                                                            1   2 (Methacrylic acid)                                                                      6,000 5      No    9.8                                 Run No. 3                                                                            1   4 (Methacrylic acid)                                                                      8,000 5      No    8.9                                 Run No. 4                                                                            1   2 (Acrylic acid)                                                                          7,000 5      No    8.7                                 Run No. 5                                                                            1   1 (Methacrylic acid)                                                                      5,000 3      No    7.5                                 Comparative                                                                   Application                                                                   Example 4                                                                     Run No. 6                                                                            No addition     --    0      Yes   0.4                                 Run No. 7                                                                            Poly(sodium acrylate)                                                                         3,000 5      Yes   3.5                                 __________________________________________________________________________

Application Example 6 and Comparative Application Example 5 Run No. 1

A polyester woven cloth was cut into a size of 8×10 cm, washed withdistilled water for 2 hours at 100° C., and dried under reducedpressure. The resulting cloth was immersed in an aqueous solutioncontaining 10% of MBSN (Example 1) and 0.1% of ammonium persulfate, at25° C. After one hour of immersion, the cloth was pulled up andinterposed between two sheets of filter paper to remove the excessivesolution adhering on the cloth surface.

The amount of solution absorbed by the cloth was 20.5% based on theweight of the cloth. The cloth was placed in a bag made of aluminumfoil. The bag was purged with nitrogen.

The bag was interposed between two plates of a press of 120° C. andheated for 10 minutes. Then, the cloth was taken out of the bag and keptin boiling water of 100° C. for 2 hours to remove the unreacted monomerand non-grafted water-soluble polymers. The weight increase by thistreatment was 1.22%.

The treated cloth was soft, had good texture and showed no coloring.

The treated woven cloth had excellent water absorbency and excellentantistatic property. With respect to water absorbency, the untreatedpolyester woven cloth (Comparative Application Example 5 ) absorbedlittle water even 300 seconds after the falling of waterdrops on thecloth, while the treated cloth absorbed waterdrops completely in 23.1seconds. With respect to the anti-static property, the untreated cloth(Comparative Application Example 5 ) showed a static voltage of 5,000 Vand its half-life of more than 1,800 seconds, while the treated clothshowed 510 V and 3.5 seconds.

Run Nos. 2 to 5

Using the monomer compositions shown in Table 6, the same tests as inRun No. 1 were conducted. The results are shown in Table 6 together withthose of Run No. 1.

Comparative Application Examples 6 and 7

The same polyester woven cloth as used in Application Example 6 wastreated in the same manner as in Application Example 6, using sodiumvinylsulfonate and sodium allylsulfonate.

The weight increase was 0.11% and 0.32%, respectively. Each of thetreated cloths was measured for water absorbency and antistaticproperty. The results are shown in Table 6 together with those ofApplication Example 6.

As is clear from Table 6, the cloths treated with the fiber-treatingagents of this invention show superior antistatic property and superiorhydrophilic property.

                                      TABLE 6                                     __________________________________________________________________________           Monomer composition      Half-life                                                                          Time                                            charged in production    of   required                                        of copolymer    Weight                                                                             Static                                                                            static                                                                             for water                                       (mole ratio)    increase                                                                           voltage                                                                           voltage                                                                            absorption                                      MBSN                                                                              Second treating agent                                                                     (%)  (V) (sec)                                                                              (sec)                                    __________________________________________________________________________    Application                                                                   Example 6                                                                     Run No. 1                                                                            10  0           1.22 510 3.5  23.1                                     Run No. 2                                                                            5   5 (Acrylic acid)                                                                          1.68 750 7.9  18.1                                     Run No. 3                                                                            5   5 (Methacrylic acid)                                                                      1.15 675 4.5  30.7                                     Run No. 4                                                                            5   5 (Acrylamide)                                                                            1.07 800 10.5 45.0                                     Run No. 5                                                                            5   5 (PEGMA-14G)                                                                             1.75 450 2.9  19.0                                     Comparative                                                                          0   0           0    5,000                                                                             1,800                                                                              Above 300                                Application                                                                   Example 5                                                                     Comparative                                                                          10 (Sodium vinylsulfonate)                                                                    0.11 4,500                                                                             1,300                                                                              210                                      Application                                                                   Example 6                                                                     Comparative                                                                          10 (Sodium allylsulfonate)                                                                    0.32 3,100                                                                               950                                                                              250                                      Application                                                                   Example 7                                                                     __________________________________________________________________________

Application Example 7

17 g of a triphenylmethane type dye (C.I. No. Basic Blue 5) representedby the following formula: ##STR8## 17 g of a copolymer of a MBSN(produced in accordance with Example 2) and acrylic acid [weight-averagemolecular weight=10,000, MBSN/acrylic acid=4/1 (by weight)], 46 g ofwater and 10 g of ethylene glycol were mixed by a sand mill to obtain auniform, liquid basic dye composition.

In 1,000 parts of a dyeing bath containing 1.8 parts of the above liquidbasic dye composition, 0.1 part of acetic acid and 0.05 part of sodiumacetate was immersed 20 parts of an acrylic fiber cloth (Vonnel 10manufactured by Mitsubishi Rayon Co., Ltd.) at 30° C.

The bath temperature was elevated to 80° C. and kept at that temperaturefor 10 minutes.

The bath temperature was then increased to 100° C. in 20 minutes and thecloth was dyed for 60 minutes. The dyed cloth was water-washed accordingto a conventional method, soaped and dried. This dyeing gave a blue dyedcloth with excellent level-dyeing and excellent dyeing affinity (degreeof exhaustion=93%).

Application Example 8 Run No. 1

Using a plating bath having the following composition, an iron substrateof 20×20×0.16 cm was nickel-plated under the conditions shown in Table7. The results are shown in Table 7.

    ______________________________________                                        Composition of plating bath                                                   ______________________________________                                        Nickel sulfate          80 g/liter                                            Nickel chloride         70                                                    Boric acid              43.8                                                  Ferrous sulfate          9.4                                                  Saccharin                1.5                                                  MBSN polymer (Example 1)                                                                               3.5                                                  Sodium borofluoride     12                                                    pH                       2.9                                                  Plating temperature (°C.)                                                                      30                                                    ______________________________________                                    

The plated surface had good gloss. The film formed by plating hadexcellent ductility and could be bent even at a radius smaller than 2.5cm without producing cracks.

Run Nos. 2 and 3

Plating was effected in the same manner as in Run No. 1, except that theplating bath composition and the plating conditions were changed asshown in Table 7. The results are shown in Table 7.

Comparative Application Example 8

Plating was effected in the same manner as in Application Example 8, RunNo. 1, except that no MBSN polymer was used. The results are shown inTable 7. The plated surface had uneven gloss, and the film formed byplating was thin and caused cracks when bent at a radius of 2.5 cm.

                                      TABLE 7                                     __________________________________________________________________________                                      Comparative                                                 Application Example 8                                                                           Application                                                 Run No. 1                                                                           Run No. 2                                                                           Run No. 3                                                                           Example 8                                   __________________________________________________________________________    Plating conditions                                                            Nickel sulfate (g/liter)                                                                      80    75    100   80                                          Nickel chloride (g/liter)                                                                     70    75    60    70                                          Boric acid (g/liter)                                                                          43.8  45.0  35.0  43.8                                        MBSN polymer (g/liter)                                                                        35    2.0   6.0   0                                           Bath temperature (°C.)                                                                 30    45    20    30                                          Plating time (min)                                                                            20    10    60    20                                          Cathode current density (A/dm.sup.2)                                                          10    10    3     10                                          Evaluation                                                                    Uniformity of glass                                                                           ◯                                                                       ◯                                                                       ◯                                                                       X                                           Uniformity of electrodeposition                                                               ◯                                                                       Δ                                                                             ◯                                                                       Δ                                     Smoothness      ◯                                                                       ◯                                                                       ◯                                                                       Δ                                     Overall rating  ⊚                                                                    ◯                                                                       ⊚                                                                    X                                           __________________________________________________________________________     Note:                                                                         ⊚ Excellent                                                    ◯ Better                                                          Δ Good                                                                  X Not good                                                               

Application Example 9 and Comparative Application Example 9

Eight kinds of muddy water were prepared by mixing 100 parts of water, 8parts of bentonite and 0.03 part of an excavation-muddywater-viscosity-adjusting agent (A, B, C or D obtained from a monomercomposition shown in Table 8 in the same manner as in Example 1 or X, Yor Z which are known agents for the same purpose).

To each muddy water was added 2 parts of portland cement, and themixture was stirred for 5 minutes at 5,000 rpm by turbine blades andallowed to stand. After 5 and 30 minutes, each mixture was measured forfunnel viscosity. The results are shown in Table 8.

                                      TABLE 8                                     __________________________________________________________________________           Type of                               Funnel viscosity (min)                  muddy water-                                                                         Polymerization conditions                                                                         Weight-                                                                             Amount                                                                             5 min 30 min                            viscosity-                                                                           First    Second     average                                                                             of   after after                             adjusting                                                                            monomer  monomer    molecular                                                                           acid addition                                                                            addition                          agent  Type                                                                              Amount                                                                             Type  Amount                                                                             weight                                                                              (meq/g)                                                                            of cement                                                                           of cement                  __________________________________________________________________________    Application                                                                   Example 9                                                                     Run No. 1                                                                            A      MBSN                                                                              2 g  Acrylic                                                                             8 g  45,000                                                                              9.6  23    29                         Run No. 2                                                                            B      MBSN                                                                              10 g  --   --   30,000                                                                              5.7  28    39                         Run No. 3                                                                            C      MBSN                                                                              8 g  Acrylamide                                                                          2 g  25,000                                                                              4.1  27    35                         Run No. 4                                                                            D      MBSN                                                                              2 g  NaSS  8 g  157,000                                                                             4.5  29    41                         Comparative                                                                   Application                                                                   Example 9                                                                     Run No. 1                                                                            X      Sodium hexametaphosphate                                                                          --    --   Above 100                                                                           Above 100                  Run No. 2                                                                            Y      Poly(sodium acrylate)                                                                             10,000                                                                              10.6 56    Above 100                  Run No. 3                                                                            Z      Sodium liguinsulfonate                                                                             6,000                                                                              3.2  Above 100                                                                           Above 100                  Run No. 4                                                                            --       --                --    --   Above 100                                                                           Above                      __________________________________________________________________________                                                       100                         NaSS: Sodium styrenesulfonate                                            

Application Example 10

Run No. 1

400 g of cyclohexane and 5 g of sorbitan monostearate were fed to a1-liter four-necked separable flask equipped with a stirrer, a refluxcondenser, a dropping funnel and a nitrogen blowing tube, and the latterwas dissolved in the former. Nitrogen gas was blown into the flask toexpel the oxygen dissolving in the solution. The solution temperaturewas elevated to 70° C. in a nitrogen gas atmosphere.

Separately, in a 500-ml dropping funnel were placed 20 g of the MBSN ofExample 1 and 80 g of acrylic acid completely neutralized with sodiumhydroxide with ice-cooling. Thereto were added 0.1 g ofN,N'-methylenebisacrylamide and 0.3 g of ammonium persulfate. Water wasadded to obtain 300 ml of an aqueous solution.

The contents in the dropping funnel was added to the contents in thefour-necked separable flask. The resulting mixture was subjected topolymerization for 1 hour at 70° C. with stirring at 300 rpm.

After the completion of the polymerization, the stirring was stopped.Swollen polymer particles precipitated on the bottom of the flask. Bydecantation was obtained a swollen polymer (a water-absorbentcrosslinked product). It was dried under reduced pressure to obtain aneasily grindable polymer. The polymer was measured for water absorbencyand the results are shown in Table 9.

The water absorbency was measured according to the following testmethods.

Pure water-absorbency

One liter of pure water was placed in a 1-liter beaker. Therein wasimmersed a paper bag of 12×10 cm containing about 50 mg of a polymer,for 24 hours at 20° C. The weight of the paper bag after immersion wasweighed, and the pure water absorbency of the polymer was calculatedfrom the following equation:

    ______________________________________                                        Absorbency (g/g polymer) =                                                    [weight of paper bag after immersion (g) -                                    weight of fed polymer (g) - weight of polymer-                                free paper bag after immersion (g)] ÷ weight                              of fed polymer (g)                                                            ______________________________________                                    

Aqueous sodium chloride absorbency

This was measured by repeating the same procedure as above, except that1 liter of a 0.9% aqueous sodium chloride solution was used in place ofthe 1 liter of pure water.

Aqueous calcium chloride (CaCl₂) absorbency

This was measured by repeating the same procedure as in the measurementof pure water absrobency, except that 1 liter of a 0.9% aqueous calciumchloride solution was used in place of the 1 liter of pure water.

Run No. 2

Polymerization and a post-treatment were effected by repeating the sameprocedure as in Run No. 1, except that 20 g of the poly(sodiumisoprenesulfonate) obtained in Example 1 was used in place of the 20 gof MBSN in Run No. 1.

The obtained polymer (water-absorbent crosslinked product) was a powdercontaining easily grindable lumps. The results of the water absorptiontest of the polymer are shown in Table 9.

Run No. 3

Polymerization and post-treatment were effected by repeating the sameprocedure as in Run No. 1, except that 80 g of methacrylic acidcompletely neutralized with ice-cooling was used in place of the 80 g ofacrylic acid completely neutralized.

The obtained polymer (water-absorbent crosslinked product) was a powdercontaining easily grindable lumps. The results of the water absorptiontest of the polymer are shown in Table 9.

Comparative Application Example 10

A polymer was obtained by repeating the same procedure as in ApplicationExample 10, Run No. 1, except that 100 g of acrylic acid was used inplace of the 20 g of MBSN and 80 g of acrylic acid. The results of thewater absorption test of the polymer are shown in Table 9.

Comparative Application Example 11

Polymerization and post-treatment were effected by repeating the sameprocedure as in Application Example 10, except that 100 g of methacrylicacid completely neutralized with ice-cooling was used in place of theacrylic acid and that 0.1 g of diethylene glycol diacrylate was used inplace of the 0.1 g of N,N'-methylenebisacrylamide. The obtained polymerwas a powder containing easily grindable lumps. The results of the waterabsorption test of the polymer are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                                      Water absorbency                                                              (g/g polymer)                                                                         Aqueous                                                               Pure    sodium   Aqueous                                                      Water   chloride CaCl.sub.2                                     ______________________________________                                        Application                                                                             Run No. 1 850       63     22                                       Example 10                                                                              Run No. 2 820       60     25                                                 Run No. 3 980       70     17                                       Comparative Application                                                                       650       65        6                                         Example 10                                                                    Comparative Application                                                                       350       43        7                                         Example 11                                                                    ______________________________________                                    

As is clear from Table 9, the water-absorbent crosslinked products ofthis invention have high water absorbency and, particularly when sodiumchloride or calcium chloride (polyvalent ion) is present in water, showclearly higher water absorbency than the Comparative ApplicationExamples.

Application Example 11

Run No. 1

A rubber compound was obtained by kneading, on a 6-inch. roll, thefollowing materials with the water-absorbent crosslinked productsynthesized in Application Example 10, Run No. 1. This compound wassubjected to press cure at 145° C. for 25 minutes to obtain a sheet of 2mm in thickness.

The sheet was subjected to tensile test by JIS K 6301 and pure waterabsorbency test. The latter test was conducted in the same manner as inthe above pure water absorbency test, except that immersion wasconducted for 5 days at 20° C. The results are shown in Table 10.

    ______________________________________                                        Compounding recipe                                                            ______________________________________                                        Natural rubber          100 parts                                             Zinc white               5                                                    Stearic acid             1                                                    HAF carbon black         30                                                   Calcium carbonate        30                                                   Sulfur                   1                                                    N-cyclohexyl-2-benzothiazole-                                                                          1.5                                                  sulfenamide                                                                   Water-absorbent crosslinked                                                                            50                                                   product                                                                       ______________________________________                                    

Run No. 2

A rubber compound was obtained using the same compounding recipe as inApplication Example 11, Run No. 1, except that the water-absorbentcrosslinked product synthesized in Application Example 10, Run No. 2 wasused in place of the water-absorbent crosslinked product synthesized inApplication Example 10, Run No. 1. The compound was subjected to thesame tests as in Run No. 1.

The results are shown in Table 10.

Comparative Application Example 12

A rubber compound was obtained using the same compounding recipe as inApplication Example 11, Run No. 1, except that the water-absorbentcrosslinked product synthesized in Comparative Application Example 10was used in place of the water-absorbent crosslinked polymer synthesizedin Application Example 10, Run No. 1. The compound was subjected to thesame tests as in Application Example 10, Run No. 1.

The results are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                                     Tensile test Pure water                                                       Tensile Elonga-  absorbency                                                   strength                                                                              tion     (g/g                                                         (kgf/cm.sup.2)                                                                        (%)      composition)                                    ______________________________________                                        Application                                                                            Run No. 1 105       820    1.3                                       Example 11                                                                             Run No. 2 120       750    1.0                                       Comparative Application                                                                       55       780      0.3                                         Example 12                                                                    ______________________________________                                    

What is claimed is:
 1. A water-soluble polymer having at least one ofthe recurring structural units represented by the formulas (III), (IV)and (V) obtained by subjecting a monomer represented by the formula (I)to polymerization: ##STR9## wherein R¹, R², R³, R⁵, and R⁶, which be thesame or different, represent hydrogen atoms or an --SO₃ X group (Xrepresents a hydrogen atom, a metal atom, an ammonium group or aquaternary ammonium group); wherein one of said R¹, R², R³, R⁵ and R⁶ isan --SO₃ X group; and wherein R⁴ is a hydrogen atom or a methyl group,wherein said water-soluble polymer has a poly(sodiumstyrenesulfonate)-reduced weight average molecular weight of 500 to5,000,000.
 2. The water-soluble polymer of claim 1, having a poly(sodiumstyrenesulfonate)-reduced weight average molecular weight of 1,000 to500,000.
 3. A water-soluble, dispersing agent, having at least one ofthe recurring structural units represented by the formulas (III), (IV)and (V) obtained by subjecting a monomer represented by the formula (I)to polymerization: ##STR10## wherein R¹, R², R³, R⁵, and R⁶, which maybe the same or different, represent hydrogen atoms or an --SO₃ X group(X represents a hydrogen atom, a metal atom, an ammonium group or aquaternary ammonium group); wherein one of said R¹, R², R³, R⁵ and R⁶ isan --SO₃ X group; and wherein R⁴ is a hydrogen atom or a methyl group,wherein said dispersing agent has poly(sodium sytrenesulfonate)-reducedweight average molecular weight of 500 to 5,000,000.
 4. A water-soluble,water-treating agent, having at least one of the recurring structuralunits represented by the formulas (III), (IV) and (V) obtained bysubjecting a monomer represented by the formula (I) to polymerization:##STR11## wherein R¹, R², R³, R⁵, and R⁶, which may be the same ordifferent, represent hydrogen atoms or an --SO₃ X group (X represents ahydrogen atom, a metal atom, an ammonium group or a quaternary ammoniumgroup); wherein one of said R¹, R², R³, R⁵ and R⁶ is an --SO₃ X group;and wherein R⁴ is a hydrogen atom or a methyl group, wherein saidwater-treating agent has a poly(sodium sytrenesulfonate)-reduced weightaverage molecular weight of 500 to 5,000,000.
 5. A water-soluble,fiber-treating agent, having at least one of the recurring structuralunits represented by the formulas (III), (IV) and (V) obtained bysubjecting a monomer represented by the formula (I) to polymerization:##STR12## wherein R¹, R², R³, R⁵, and R⁶, which may be the same ordifferent, represent hydrogen atoms or an --SO₃ X group (X represents ahydrogen atom, a metal atom, an ammonium group or a quaternary ammoniumgroup); wherein one of said R¹, R², R³, R⁵ and R⁶ is an --SO₃ X group;and wherein R⁴ is a hydrogen atom or a methyl group, wherein saidfiber-treating agent has a poly(sodium sytrenesulfonate)-reduced weightaverage molecular weight of 500 to 5,000,000.
 6. A water-soluble platingbath additive, having at least one of the recurring structural unitsrepresented by the formulas (III), (IV) and (V) obtained by subjecting amonomer represented by the formula (I) to polymerization: ##STR13##wherein R¹, R², R³, R⁵, and R⁶, which may be the same or different,represent hydrogen atoms or an --SO₃ X group (X represents a hydrogenatom, a metal atom, an ammonium group or a quaternary ammonium group);wherein one of said R¹, R², R³, R⁵ and R⁶ is an --SO₃ X group; andwherein R⁴ is a hydrogen atom or a methyl group, wherein said platingbath additive has a poly(sodium sytrenesulfonate)-reduced weight averagemolecular weight of 500 to 5,000,000.
 7. A water-soluble,excavation-muddy water-viscosity-adjusting agent, having at least one ofthe recurring structural units represented by the formulas (III), (IV)and (V) obtained by subjecting a monomer represented by the formula (I)to polymerization: ##STR14## wherein R¹, R², R³, R⁵, and R⁶, which maybe the same or different, represent hydrogen atoms or an --SO₃ X group(X represents a hydrogen atom, a metal atom, an ammonium group or aquaternary ammonium group); wherein one of said R¹, R², R³, R⁵ and R⁶ isan --SO₃ X group; and wherein R⁴ is a hydrogen atom or a methyl group,wherein said agent has a poly(sodium sytrenesulfonate)-reduced weightaverage molecular weight of 500 to 5,000,000.